CN103562240A - Method for continuous production of water-absorbent polymer particles - Google Patents
Method for continuous production of water-absorbent polymer particles Download PDFInfo
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- CN103562240A CN103562240A CN201280025097.0A CN201280025097A CN103562240A CN 103562240 A CN103562240 A CN 103562240A CN 201280025097 A CN201280025097 A CN 201280025097A CN 103562240 A CN103562240 A CN 103562240A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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- C08F216/34—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an aldehydo radical
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08L2312/00—Crosslinking
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Abstract
A method for the continuous production of water-absorbent polymer particles, wherein the acrylic acid used for producing the polymer particles has a low purity.
Description
The present invention relates to a kind of method of continuous production of water-absorbent polymer, wherein the vinylformic acid for the preparation of this polymer beads has low purity.
Water-absorbing polymeric particles is for the production of diaper, tampon, cotton wool and other hygienic articles, and can be used as the water-holding agent in commodity gardening.Water-absorbing polymeric particles is also referred to as super-absorbent.
The preparation of water-absorbing polymeric particles is recorded in monograph " Modern Superabsorbent Polymer Technology ", F.L.Buchholz and A.T.Graham, Wiley-VCH, 1998, the 71-103 pages.
The amount that the performance of water-absorbing polymeric particles can for example be passed through used linking agent regulates.Along with the increase of dosage of crosslinking agent, centrifugal retention volume (CRC) reduces and at 21.0g/cm
2absorbed dose under pressure (AUL0.3psi) is through a maximum value.
In order to improve use properties, for example, the perviousness (SFC) of the gel bed of swelling and at 49.2g/cm in diaper
2pressure under absorbed dose (AUL0.3psi), water-absorbing polymeric particles carries out behind surface crosslinked conventionally.This has increased the degree of crosslinking of particle surface, and it can remove 49.2g/cm at least partly
2pressure under absorbed dose (AUL0.3psi) and centrifugal retention volume (CRC) associated.This surface is crosslinked can carrying out in mutually at aqueous gel afterwards.Yet, preferably, dry, polymer beads (base polymer) that grind and sieve surface are cross-linked with the rear linking agent coating in surface and after making its hot surface.The linking agent that is suitable for this object is to form with at least two carboxylate group of water-absorbing polymeric particles the compound of covalent linkage.
An object of the present invention is to provide a kind of improved method of preparing water-absorbing polymeric particles, more specifically, a kind of method that wherein also can use the monomer of relatively high pollution.
This object realizes by a kind of method of continuous production of water-absorbent polymer, and described method comprises that by a kind of monomer solution or suspension polymerization, to obtain polymer gel, described monomer solution or suspension comprise:
The vinylformic acid that a) can be neutralized at least partly,
B) at least one linking agent,
C) at least one initiator,
D) optionally one or more can with the ethylenically unsaturated monomers of acrylic acid copolymer and
E) one or more water-soluble polymerss optionally,
The polymer gel of gained is dry, dry polymer gel is pulverized to obtain polymer beads and by the polymer beads classification of gained, wherein vinylformic acid is without interruption, and vinylformic acid without interruption has and is less than the purity of 99.8 % by weight and acrylic acid purity without interruption changed and is less than 2 % by weight in 24 hours.
Acrylic acid purity without interruption is preferably 80 to 99.5 % by weight, more preferably 90 to 99 % by weight and most preferably 95 to 98 % by weight.The variation of vinylformic acid without interruption purity in 24 hours is preferably lower than 1 % by weight, more preferably less than 0.5 % by weight and most preferably lower than 0.2 % by weight.
Acrylic acid purity without interruption is that 100 % by weight deduct and in vinylformic acid preparation process, residue in the impurity in vinylformic acid, and passes through gas chromatography determination.For this reason, from 100 % by weight, deduct detected impurity.It should be noted that the water being present in vinylformic acid can not pass through gas chromatography determination here.Therefore, water-content can only independent measurement, for example, by Karl Fischer volumetry, and must be subtracted equally.Purity by Propylene By Gas Chromatography acid is also recorded in monograph " Modern Superabsorbent Polymer Technology ", F.L.Buchholz and A.T.Graham, and Wiley-VCH, in 1998, the 121 pages.
The present invention is based on the discovery that the effect of single impurity in preparing water-absorbing polymeric particles can compensate by suitable measure.In order to realize constant quality product in successive processes, the concentration that therefore only needs to keep impurity is substantially constant in time.Therefore in continuous production, needn't constantly regulate the measure of compensated impurity.
Therefore the method according to this invention can be used through the vinylformic acid of complicated purification not too, and it is more cheap therefore to prepare water-absorbing polymeric particles.
Possible impurity can be divided into roughly regulates impurity, inhibition of impurities, crosslinked impurity and inert impurities, and these impurity can be classified based on its effect in tentative experiment.
Regulate impurity to increase and start new polymeric chain by termination polymer chain and intervene polymerization kinetics.This causes the increase of centrifugal retention volume (CRC) and extractable content.Meanwhile, under pressure, absorbed dose (AUL0.3psi) reduces.Regulate the effect of impurity can be for example by increase linking agent b) amount compensate.This impurity can be, for example, and propenal, vinyl carbinol, Virahol, furans-2-formaldehyde (2-furfural) and phenyl aldehyde.
Inhibition of impurities stops or the polyreaction that slows down.The effect of inhibition of impurities can be for example by increasing initiator c) amount compensate.This impurity can be, for example, and quinhydrones and thiodiphenylamine.
Crosslinked impurity increases the degree of crosslinking in polymerization.This causes the reduction of centrifugal retention volume (CRC) and extractable content.Meanwhile, under pressure, absorbed dose (AUL0.3psi) increases.The effect of crosslinked impurity can be for example by reduction linking agent b) amount compensate.This impurity can be, for example allyl acrylate and allyl methacrylate(AMA).
Inert impurities is---if any---only less on the impact of polymerization.This impurity can be, for example, and water, acetic acid and propionic acid.
The method according to this invention can be used through the vinylformic acid of complicated purification not too.Important only, the concentration changes with time of the impurity existing in vinylformic acid used is very little.For example, can carry out purifying propenoic acid by short rectifying column, and can obtain in a simple manner and there is the allyl acrylate of high-content and the vinylformic acid of other impurity.Then can make polymerization adapt to this vinylformic acid quality by simple tentative experiment.Then, rectifying itself can be monitored based on guiding component (as acetic acid), and it means that rectifying keeps constant mode to operate with guiding component concentration.
In a particularly preferred embodiment of the present invention, vinylformic acid without interruption comprises
-at least 0.0005 % by weight, preferred at least 0.001 % by weight, more preferably at least 0.002 % by weight and most preferably at least 0.0025 % by weight adjusting impurity and/or
-at least 0.00005 % by weight, preferred at least 0.0001 % by weight, more preferably at least 0.0002 % by weight and most preferably at least 0.00025 % by weight inhibition of impurities and/or
-at least 0.005 % by weight, preferred at least 0.01 % by weight, more preferably at least 0.02 % by weight and the most preferably crosslinked impurity of at least 0.025 % by weight.
In a utmost point particularly preferred embodiment of the present invention, vinylformic acid without interruption comprises
-0.0005 to 0.1 % by weight, preferred 0.001 to 0.05 % by weight, more preferably 0.002 to 0.02 % by weight and most preferably 0.0025 to 0.01 % by weight adjusting impurity and/or
-0.00005 to 0.1 % by weight, preferred 0.0001 to 0.05 % by weight, more preferably 0.0002 to 0.02 % by weight and most preferably 0.00025 to 0.01 % by weight inhibition of impurities and/or
-0.005 to 1 % by weight, preferred 0.01 to 0.5 % by weight, more preferably 0.02 to 0.2 % by weight and the most preferably crosslinked impurity of 0.025 to 0.1 % by weight.
Described impurity is especially water, acetic acid, propenal, formic acid, formaldehyde, propionic acid, furans-2-formaldehyde, furans-3-formaldehyde, phenyl aldehyde, protoanemonin (protoanemonin), maleic anhydride, toxilic acid, diacrylate, allyl acrylate, phenylformic acid, quinhydrones and/or thiodiphenylamine.
Water-absorbing polymeric particles is by preparing monomer solution or suspension polymerization, and described polymer beads is normally non-water-soluble.
Vinylformic acid and/or the ratio of its salt in monomer total amount be 50mol% at least preferably, more preferably at least 90mol% and most preferably 95mol% at least.
Vinylformic acid used comprises stopper conventionally, and preferred quinhydrones monoether, as storage stabilizing agent.
Therefore, monomer solution preferably comprises and is up to 250 ppm by weight, preferably be up to 130 ppm by weight, more preferably be up to 70 ppm by weight, and preferred at least 10 ppm by weight, more preferably at least 30 ppm by weight and particularly the quinhydrones monoether of approximately 50 ppm by weight, in each case based on unneutralized vinylformic acid meter.The vinylformic acid that for example, can have a quinhydrones monoether of appropriate amount by use is prepared this monomer solution.
Preferred quinhydrones monoether is hydroquinone monomethyl ether (MEHQ) and/or alpha-tocopherol (vitamin-E).
Suitable linking agent b) for thering are at least two compounds that are suitable for crosslinked group.This group is, for example, free redical polymerization is to the ethylenic unsaturated group in polymer chain, and can form with acrylic acid acidic group the functional group of covalent linkage.In addition, can also be suitable as linking agent b with the polyvalent metal salt that acrylic acid at least two acidic groups form coordinate bond).
Linking agent b) be preferably and there are at least two free redical polymerizations to the compound of the polymerizable groups of polymer network.Suitable linking agent b) be, for example,, as the ethylene glycol dimethacrylate of being recorded in EP0530438A1, diethylene glycol diacrylate, polyethyleneglycol diacrylate, allyl methacrylate(AMA), Viscoat 295, triallylamine, tetra allyl ammonium chloride, tetraene propoxy-ethane; As diacrylate and the triacrylate recorded in EP0547847A1, EP0559476A1, EP0632068A1, WO93/21237A1, WO2003/104299A1, WO2003/104300A1, WO2003/104301A1 and DE10331450A1; As what recorded in DE10331456A1 and DE10355401A1, not only comprise the mixing acrylate that acrylate group also comprises other ethylenic unsaturated groups; Or as the linking agent mixture of being recorded in for example DE19543368A1, DE19646484A1, WO90/15830A1 and WO2002/032962A2.
Preferred linking agent b) be tetramethylolmethane base triallyl ether, tetraene propoxy-ethane, methylene-bis Methacrylamide, 15 heavy ethoxylated trimethylolpropane triacrylates, polyethyleneglycol diacrylate, Viscoat 295 and triallylamine.
Extremely particularly preferred linking agent b) for acrylic or methacrylic acid esters to obtain polyethoxylated and/or the poly-propoxylated glycerol of diacrylate or triacrylate, as recorded in WO2003/104301A1 for example.Particularly advantageously diacrylate and/or the triacrylate of 3 to 10 heavy ethoxylated glycerols.The utmost point is 1 to 5 heavily diacrylate or the triacrylate of ethoxylation and/or propoxylated glycerol particularly preferably.3 to 5 heavily triacrylates of ethoxylation and/or propoxylated glycerol, the particularly triacrylate of 3 heavy ethoxylated glycerols most preferably.
Linking agent b) amount is preferably 0.05 to 1.5 % by weight, and more preferably 0.1 to 1 % by weight and most preferably 0.2 to 0.6 % by weight, in each case based on vinylformic acid meter.Along with the increase of dosage of crosslinking agent, centrifugal retention volume (CRC) reduces and at 21.0g/cm
2pressure under absorbed dose through a maximum value.
Initiator c used) can be all compounds that produce free radical under polymerizing condition, for example, thermal initiator, redox initiator, light trigger.Suitable redox initiator is Sodium persulfate/xitix, hydrogen peroxide/xitix, Sodium persulfate/sodium bisulfite and hydrogen peroxide/sodium bisulfite.Preferably use the mixture of thermal initiator and redox initiator, as Sodium persulfate/hydrogen peroxide/xitix.Yet reduction components used is preferably the sodium salt of 2-hydroxyl-2-sulfinyl acetic acid, the disodium salt of 2-hydroxyl-2-alkylsulfonyl acetic acid and the mixture of sodium bisulfite.This mixture can be used as
with
(Br ü ggemann Chemicals; Heilbronn; Germany) obtain.
Can with the ethylenically unsaturated monomers d of acrylic acid copolymer) be, for example, acrylamide, Methacrylamide, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, dimethylaminoethyl methacrylate, vinylformic acid dimethylamino ethyl ester, vinylformic acid dimethylamino propyl ester, vinylformic acid diethylamino propyl ester, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate.
Other can with the ethylenically unsaturated monomers d of acrylic acid copolymer) be that for example, ethylenic unsaturated carboxylic acid, as methacrylic acid and methylene-succinic acid, and ethylenic unsaturated sulfonic acid, as styrene sulfonic acid and 2-acrylamide-2-methylpro panesulfonic acid (AMPS).
Water-soluble polymers e used) can be polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivative, modified-cellulose (as methylcellulose gum or Natvosol), gelatin, polyglycol or polyacrylic acid, preferred starch, starch derivative and modified-cellulose.
Conventionally, use aqueous monomers solution.The water-content of this monomer solution is preferably 40 to 75 % by weight, more preferably 45 to 70 % by weight and most preferably 50 to 65 % by weight.Also can use monomer suspension, there is the monomer solution of excessive propene acid (as sodium acrylate).Along with water-content improves, energy required in drying process subsequently increases, and along with reduced water content, is just not enough to remove polymerization heat.
For best effect, preferred stopper needs dissolved oxygen.Therefore, this monomer solution can---pass into rare gas element, preferred nitrogen or carbonic acid gas---by inerting before polymerization and remove dissolved oxygen.Oxygen level in monomer solution is preferably reduced to and is less than 1 ppm by weight before polymerization, is more preferably reduced to and is less than 0.5 ppm by weight, is most preferably reduced to and is less than 0.1 ppm by weight.
Suitable reactor is for example, to mediate reactor or belt reactor.As described in WO2001/038402A1, in kneader, the polymer gel forming in the polymerization of aqueous monomers solution or suspension is pulverized continuously by for example trans revolving stirrer axle.Polymerization is on tape recorded in, and for example DE3825366A1 and US6, in 241,928.Polymerization in belt reactor has formed a kind of polymer gel, and it need at another method steps, for example, be pulverized in forcing machine or kneader.
In order to improve drying property, also the polymer gel of the pulverizing obtaining by kneader can be extruded in addition.
Yet, also can make aqueous monomers solution droplets and by the polymerization in a kind of carrier gas air-flow of heat of the drop of gained.Polymerization and drying means step can be combined, described at WO2008/040715A2 and WO2008/052971A1 herein.
The acid groups of the polymer gel of gained is partially neutralized conventionally.Neutralization is preferably carried out in monomer stage.This is conventionally by sneaking into for aqueous solution form or preferably also for the neutralizing agent of solid form completes.Degree of neutralization is preferably 25 to 95mol%, and more preferably 30 to 80mol%, and most preferably 40 to 75mol%, to this, can use conventional neutralizing agent, preferred alkali metal hydroxide, alkalimetal oxide, alkaline carbonate or alkali metal hydrocarbonate and composition thereof.Also can use ammonium salt to replace an alkali metal salt.Particularly preferred basic metal is sodium and potassium, but the utmost point particularly preferably sodium hydroxide, sodium carbonate or sodium bicarbonate and composition thereof.
Yet, also can be after polymerization, the stage that forms polymer gel in polymerization neutralizes.Also can before polymerization, by actual interpolation part neutralizing agent in monomer solution, neutralize and be up to 40mol%, preferably 10 to 30mol% and more preferably 15 to 25mol% acid groups, and only after polymerization, in polymer gel stage, set required final degree of neutralization.When polymer gel is neutralized at least in part after polymerization, preference as by forcing machine by polymer gel mechanical disintegration, in the case, neutralizing agent can be injected into, drench into or pour into and carefully mix subsequently.For this reason, the gelatinous mass obtaining can be extruded with homogenizing repeatedly.
Polymer gel is preferably dry with belt dryer subsequently, until remaining moisture content is preferably 0.5 to 15 % by weight, more preferably 1 to 10 % by weight and most preferably 2 to 8 % by weight, the test method No.WSP230.2-05 that described remaining moisture content is recommended by EDANA " Mass Loss Upon Heating " measures.In the situation that remaining moisture content is too high, dry polymer gel has too low second-order transition temperature T
g, and it is very difficult further to process meeting.In the situation that remaining moisture content is too low, dry polymer gel is too crisp, and in pulverising step subsequently, obtains the too small polymer beads of a large amount of undesired particle diameters (" fine powder ").Before dry, the solids content of gel is preferably 25 to 90 % by weight, more preferably 35 to 70 % by weight and most preferably 40 to 60 % by weight.Yet, optionally, also fluidized bed dryer or pedal-type dryer can be used for to drying purpose.
After this, dry polymer gel is pulverized and classification, and can be single-stage or multistage roller mill conventionally for the device grinding, preferably two-stage or three grades of roller mills, needle mill, hammer mill or oscillating mills.
The median size of the polymer beads shifting out as product fraction is preferably at least 200 μ m, and more preferably 250 to 600 μ m and the utmost point are in particular 300 to 500 μ m.The test method No.WSP220.2-05 that the median size of product fraction can be recommended by EDANA " Particle Size Distribution " measures, and wherein the mass ratio of sieve fraction is determined by figure with form mapping and the median size of accumulation.Median size is the value that obtains accumulating the mesh size of 50 % by weight herein.
The ratio with the particle that is greater than 150 μ m particle diameters is preferably at least 90 % by weight, more preferably at least 95 % by weight and most preferably at least 98 % by weight.
The polymer beads that particle diameter is too little reduces perviousness (SFC).Therefore, the ratio of too small polymer beads (" fine powder ") should be very low.
Therefore, too small polymer beads is conventionally removed and is recycled in the method.Preferably before polymerization, carried out before dry polymer gel in polymerization process or after polymerization at once.Too small polymer beads can be before recirculation or in process recycling water and/or aqueous tenside moistening.
Also can be in subsequent method step for example on surface, after crosslinked or another application step, remove too small polymer beads afterwards.In this case, the too small polymer beads of recirculation is that behind surface, be cross-linked or coated in another way, for example, by pyrogenic silica, applied.
When kneading reactor is used to polymerization, too small polymer beads preferably adds in the rear three/one-phase of polymerization.
When too small polymer beads added in the stage very early, for example, actual while adding in monomer solution, this has reduced the centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained.Yet, this can be for example by regulating linking agent b used) amount compensate.
For example, for example, while---just adding (being added in a forcing machine) until be connected to the device in the downstream of polymerization reactor---when too small polymer beads added in the very late stage, too small polymer beads is difficult to bring in the polymer gel of gained.But insufficient too small polymer beads of including in is again isolated in process of lapping from dry polymer gel, therefore in classification process, be again removed, and increased the amount of the too small polymer beads for the treatment of recirculation.
Have particle diameter at the most the particle ratio of 850 μ m be preferably at least 90 % by weight, more preferably at least 95 % by weight, most preferably at least 98 % by weight.
Have particle diameter at the most the particle ratio of 600 μ m be preferably at least 90 % by weight, more preferably at least 95 % by weight, most preferably at least 98 % by weight.
The excessive polymer beads of particle diameter has reduced free swell rate.Therefore, the ratio of excessive polymer beads equally should be very little.
Therefore, excessive polymer beads is conventionally removed and is recycled in the grinding of dry polymer gel.
In order further to improve performance, polymer beads surface is crosslinked afterwards.Behind suitable surface, linking agent is to comprise to form with at least two carboxylate groups of polymer beads the compound of the group of covalent linkage.Suitable compound is, for example, and the polyfunctional amine of recording in EP0083022A2, EP0543303A1 and EP0937736A2, multifunctional amide amine, multi-functional epoxy's compound; Two functional alcohol or the polyfunctional alcohol that in DE3314019A1, DE3523617A1 and EP0450922A2, record; Or at DE10204938A1 and US6, the beta-hydroxyalkylamides of recording in 239,230.
Behind the suitable surface of the conduct of other records, linking agent is the cyclic carbonate in DE4020780C1; 2-oxazolidone in DE19807502A1 and derivative thereof are as 2-hydroxyethyl-2-oxazolidone; In DE19807992C1 two-2-oxazolidone and many-2-oxazolidone; 2-oxo tetrahydrochysene-1 in DE19854573A1,3-oxazine and derivative thereof; N-acyl group-2-oxazolidine ketone in DE19854574A1; Ring-type urea in DE10204937A1; Bicyclic amide acetal in DE10334584A1; Morpholine-2 in trimethylene oxide in EP1199327A2 and ring-type urea and WO2003/031482A1,3-diketone and derivative thereof.
Behind preferred surface, linking agent is the reaction product of ethylene carbonate, ethylene glycol diglycidylether, polymeric amide and Epicholorohydrin and the mixture of propylene glycol and BDO.
Behind extremely particularly preferred surface, linking agent is 2-hydroxyethyl-2-oxazolidone, 2-oxazolidone and 1,3-PD.
In addition, also can use linking agent behind the surface that comprises other polymerisable ethylenic unsaturated group described in DE3713601A1.
Behind surface, the amount of linking agent is preferably 0.001 to 2 % by weight, and more preferably 0.02 to 1 % by weight and most preferably 0.05 to 0.2 % by weight, in each case based on polymer beads meter.
In a preferred embodiment of the present invention, behind surface linking agent, before surface is crosslinked afterwards, in process or afterwards polyvalent cation is applied to particle surface.
Available polyvalent cation is in the method for the invention, and for example, divalent cation is the positively charged ion of zinc, magnesium, calcium, iron and strontium for example; Tricationic is the positively charged ion of aluminium, iron, chromium, rare earth and Mn for example; Quadrivalent cation is the positively charged ion of titanium and zirconium for example.Possible counter ion are hydroxide radical, chlorion, bromide anion, sulfate radical, bisulfate ion, carbonate, bicarbonate radical, nitrate radical, phosphate radical, hydrogen phosphate, dihydrogen phosphate and carboxylate radical, for example acetate moiety, citrate and lactate.The salt with different counter ion is also passable, and for example basic aluminium salt is as single aluminum acetate or single Aluctyl.Preferably sulfuric acid aluminium, single aluminum acetate and Aluctyl.Except metal-salt, also can use polyamines as polyvalent cation.
The amount of polyvalent cation used is, for example, 0.001 to 1.5 % by weight, preferably 0.005 to 1 % by weight and more preferably 0.02 to 0.8 % by weight, in each case based on polymer beads meter.
After surperficial, be cross-linked and conventionally carry out in such a way, be about to the solution spray of the rear linking agent in surface to dry polymer beads.After spray application, the polymer beads heated drying of the rear linking agent in surface will be coated with, and behind surface, crosslinking reaction can or be carried out before dry in process.
Behind surface, the spray application of the solution of linking agent is preferably carried out in having the mixing tank of portable mixing tool, for example screw mixer, disk mixer and arm mixer.Horizontal mixing tank particularly preferably, arm mixer for example, the utmost point is vertical mixer particularly preferably.Difference between horizontal mixing tank and vertical mixer is the position of mixing axle, and horizontal mixing tank has the mixing axle that a level installs and vertical hybrid instrument has a vertically arranged mixing axle.Suitable mixing tank is, for example, horizontal
ploughshare mixing tank (Gebr.
maschinenbau GmbH; Paderborn; Germany), Vrieco-Nauta continuous mixing device (Hosokawa Micron BV; Doetinchem; The Netherlands), Processall Mixmill mixing tank (Processall Incorporated; Cincinnati; US) and Schugi
(Hosokawa Micron BV; Doetinchem; The Netherlands).Yet, also can be in fluidized-bed cross-linking agent solution after spray surface.
Behind surface, linking agent is used with the form of aqueous solution conventionally.Behind surface, the depth of penetration of linking agent in polymer beads can regulate by content and the solvent total amount of non-aqueous solvent.
When only water is as solvent, advantageously add tensio-active agent.This has improved wettability and has reduced the tendency of caking.Yet, preferably use the mixture of solvent, for example isopropanol/water, 1,3-PD/water and propylene glycol/water, wherein blending ratio is in mass preferably 20:80 to 40:60.
Heated drying preferably carries out in contact drying device, more preferably pedal-type dryer, most preferably pan dryer.Suitable moisture eliminator is, for example, and Hosokawa
horizontal pedal-type dryer (Hosokawa Micron GmbH; Leingarten; Germany), Hosokawa
pan dryer (Hosokawa Micron GmbH; Leingarten; Germany),
moisture eliminator (Metso Minerals Industries Inc.; Danville; USA) and Nara pedal-type dryer (NARA Machinery Europe; Frechen; Germany).In addition, also can use fluidized bed dryer.
Dry can be in mixing tank self by heating jacket or blow into warm air and carry out.Same suitable is to use a kind of downstream dryer, for example cabinet drier, rotary tube furnace or heatable screw rod.Particularly advantageously in fluidized bed dryer, mix and be dried.
Preferred drying temperature at 100 ℃ within the scope of 250 ℃, preferably 120 ℃ to 220 ℃, more preferably 130 ℃ to 210 ℃, most preferably 150 ℃ to 200 ℃.At this temperature, in reaction mixer or moisture eliminator, the preferred residence time is preferably at least 10 minutes, and more preferably at least 20 minutes, most preferably at least 30 minutes, and at the most 60 minutes conventionally.
In a preferred embodiment of the present invention, after heated drying, water-absorbing polymeric particles is cooling.Cooling preferably in contact water cooler, more preferably oar formula water cooler and most preferably carrying out in disc type water cooler.Suitable water cooler is, for example Hosokawa
horizontal oar formula water cooler (Hosokawa Micron GmbH; Leingarten; Germany), Hosokawa
disc type water cooler (Hosokawa Micron GmbH; Leingarten; Germany),
water cooler (Metso Minerals Industries Inc.; Danville; USA) and Nara oar formula water cooler (NARA Machinery Europe; Frechen; Germany).In addition, also can use fluidized bed cooler.
In water cooler, water-absorbing polymeric particles is cooled to 20 to 150 ℃, preferably 30 to 120 ℃, more preferably 40 to 100 ℃ and most preferably 50 to 80 ℃.
Subsequently, can be again by surface crosslinked polymer beads classification afterwards, too small and/or excessive polymer beads is removed and is recycled in the method.
In order further to improve performance, can by surface afterwards crosslinked polymer beads apply or rewetting.
Rewetting is preferably at 30 to 80 ℃, more preferably 35 to 70 ℃, more preferably carries out at 40 to 60 ℃.Crossing under low temperature, water-absorbing polymeric particles tends to caking, and under comparatively high temps, water has been evaporated to a significant degree.The amount that is used for the water of rewetting is preferably 1 to 10 % by weight, more preferably 2 to 8 % by weight and most preferably 3 to 5 % by weight.Rewetting has improved the mechanical stability of polymer beads and has reduced the tendency of its static electrification.Rewetting advantageously carries out after heated drying in water cooler.
The suitable coating that is used for improving free swell rate and perviousness (SFC) is, for example inorganic inert substance, for example water-fast metal-salt, organic polymer, cationic polymers and divalent metal or multivalent metal cation.For adhering to the suitable coating of dust, be, for example polyvalent alcohol.For eliminating the suitable coating of undesired caking tendency of polymer beads, be, pyrogenic silica for example, as
and tensio-active agent, as
The moisture content that the water-absorbing polymeric particles of preparing by the inventive method has is preferably 0 to 15 % by weight, more preferably 0.2 to 10 % by weight and most preferably 0.5 to 8 % by weight, the test method No.WSP230.2-05 that this moisture content is recommended by EDANA " Mass Loss Upon Heating " measures.
The ratio that the water-absorbing polymeric particles of preparing by the inventive method has the particle of particle diameter 300 to 600 μ m is preferably at least 30 % by weight, more preferably at least 50 % by weight and most preferably at least 70 % by weight.
The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of preparing by method of the present invention is generally at least 15g/g, preferred 20g/g at least, more preferably 22g/g at least, particularly preferably at least 24g/g and most preferably 26g/g at least.The centrifugal retention volume (CRC) of water-absorbing polymeric particles is less than 60g/g conventionally.The test method No.WSP241.2-05 that centrifugal retention volume (CRC) is recommended by EDANA " Fluid Retention Capacity in Saline, After Centrifugation " measures.
The water-absorbing polymeric particles of preparing by method of the present invention is at 49.2g/cm
2absorbed dose under pressure is generally at least 15g/g, preferred 20g/g at least, more preferably 22g/g at least, particularly preferably at least 24g/g and most preferably 26g/g at least.Water-absorbing polymeric particles is at 49.2g/cm
2absorbed dose under pressure is less than 35g/g conventionally.At 49.2g/cm
2absorbed dose under pressure is measured by the test method No.WSP242.2-05 " Absorption under Pressure, Gravimetric Determination " that is similar to EDANA recommendation, and difference is that established pressure is 49.2g/cm
2, rather than 21.0g/cm
2pressure.
Method:
Standard test methods described and called after " WSP " is recorded in hereinafter: " Standard Test Methods for the Nonwovens Industry ", 2005 editions, by " Worldwide Strategic Partners " EDANA(Avenue Eugene Plasky, 157,1030 Brussels, Belgium, www.edana.org) and INDA(1100 Crescent Green, Suite115, Cary, North Carolina27518, USA, www.inda.org) co-publicate.This publication can obtain from EDANA and INDA.
Except as otherwise noted, measurement should be carried out under the relative air humidity of the envrionment temperature of 23 ± 2 ℃ and 50 ± 10%.Before test, water-absorbing polymeric particles is fully mixed.
Centrifugal retention volume
The test method No.WSP241.2-05 that centrifugal retention volume (CRC) is recommended by EDANA " Fluid Retention Capacity in Saline, After Centrifugation " measures.
At 21.0g/cm
2absorbed dose under pressure (absorbed dose under load)
Water-absorbing polymeric particles is at 21.0g/cm
2the test method No.WSP242.2-05 that absorbed dose under pressure (AUL0.3psi) is recommended by EDANA " Absorption under Pressure, Gravimetric Determination " measures.
At 49.2g/cm
2absorbed dose under pressure (absorbed dose under load)
At 49.2g/cm
2absorbed dose under pressure (AUL0.7psi) is measured by the test method No.WSP242.2-05 " Absorption under Pressure, Gravimetric Determination " that is similar to EDANA recommendation, and difference is that established pressure is 49.2g/cm
2, rather than 21.0g/cm (AUL0.7psi)
2(AUL0.3psi).
Extractable content
The test method No.WSP270.2-05 " Extractable " that the extractable content ratio of water-absorbing polymeric particles is recommended by EDANA measures.
Acrylic acid purity
Purity testing is undertaken by having the gas chromatograph of split stream injector, and flame ionization detector.Use the J & W DB FFAB30m x 0.32mm capillary column (Agilent Technologies, Waldbronn, Germany) of film thickness 0.25 μ m.Sampler temperature is that 180 ℃ and detector temperature are 240 ℃.Select following temperature program(me): at 120 ℃ 10 minutes, with 10 ℃/min, be warming up to 220 ℃ and at 220 ℃ 15 minutes subsequently.Splitting ratio is 1: 100, and sample size is 0.5 μ l.
Temperature program(me), splitting ratio and sample size can slightly change.Need to be for its adjusting so that all components be realized to good separation and high signal to noise ratio.
With acetic acid 2-(ethyl hexyl) ester, as internal standard substance, measure.The impurity detecting deducts the impurity that detects together with the water being present in vinylformic acid with 1 factor evaluation and by 100 % by weight.Water in vinylformic acid is conventionally by Karl Fischer titration measuring.
Embodiment
In following experiment, use highly purified vinylformic acid.The impurity of being investigated can't detect in vinylformic acid used.
Embodiment 1
By 96g vinylformic acid, the 785g sodium acrylate aqueous solution (concentration 37.3 % by weight), 115g deionized water and 0.66g3 heavily ethoxylation three vinylformic acid glyceryl ester (concentration approximately 85 % by weight) by passing into nitrogen, within 30 minutes, remove atmosphericoxygen.The initiated polymerization by add 2.34g peroxy-disulfuric acid sodium water solution (concentration 10.0 % by weight), 1.50g aqueous ascorbic acid (concentration 1.0 % by weight) and 1.50g aqueous hydrogen peroxide solution (concentration 1.0 % by weight) in 2 liters of plastic containers.After 14 minutes, reach the maximum polymerization temperature (T of approximately 108 ℃
maximum).Reach T
maximumafter 60 minutes, shift out polymer gel, with mincer, use 6mm template to pulverize it, in forced ventilation loft drier, at 150 ℃, be dried 60 minutes, then the roller mill that is continuously 1000 μ m, 600 μ m and 400 μ m by gap width grinds, and the material grinding by screening and particle size range is adjusted to 150 to 850 μ m.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is that the absorbed dose (AUL0.3psi) under 40.3g/g and pressure is 7.8g/g thus.
Embodiment 2
Step is as embodiment 1, and difference is that polyreaction carries out under the existence of 100ppm allyl acrylate (based on vinylformic acid meter).The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is that the absorbed dose (AUL0.3psi) under 37.6g/g and pressure is 8.0g/g thus.
Embodiment 3
Step is as embodiment 1, and difference is that polyreaction carries out under the existence of 200ppm allyl acrylate (based on vinylformic acid meter).The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is that the absorbed dose (AUL0.3psi) under 36.3g/g and pressure is 8.4g/g thus.
Table 1: the impact of allyl acrylate (crosslinked impurity)
This form illustrates, and along with being cross-linked the increase of the amount of impurity, the absorbed dose (AUL0.3psi) under centrifugal retention volume (CRC) reduction and pressure raises.
Embodiment 4
Step is as embodiment 1, difference be that polyreaction is carried out under the existence of 100ppm allyl acrylate (based on vinylformic acid meter) and used 3 heavily the amount of ethoxylation three vinylformic acid glyceryl ester be down to 0.55g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is that the absorbed dose (AUL0.3psi) under 38.9g/g and pressure is 8.0g/g thus.
Embodiment 5
Step is as embodiment 1, difference be to be aggregated under the existence of 100ppm allyl acrylate (based on vinylformic acid meter), carry out and used 3 heavily the amount of ethoxylation three vinylformic acid glyceryl ester be down to 0.44g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is that the absorbed dose (AUL0.3psi) under 41.9g/g and pressure is 7.9g/g thus.
Table 2: the crosslinked impurity (allyl acrylate) of compensation
The impact that this form illustrates crosslinked impurity can compensate by the amount of adjusting linking agent.
Embodiment 6
By 96g vinylformic acid, the 785g sodium acrylate aqueous solution (concentration 37.3 % by weight), 115g deionized water and 0.88g3 heavily ethoxylation three vinylformic acid glyceryl ester (concentration approximately 85 % by weight) by passing into nitrogen, within 30 minutes, remove atmosphericoxygen.The initiated polymerization by add 0.78g peroxy-disulfuric acid sodium water solution (concentration 5.0 % by weight), 0.50g aqueous ascorbic acid (concentration 0.5 % by weight) and 0.50g aqueous hydrogen peroxide solution (concentration 0.5 % by weight) in 2 liters of plastic containers.After 30 minutes, reach the maximum polymerization temperature (T of approximately 106 ℃
maximum).Reach T
maximumafter 60 minutes, shift out polymer gel, with mincer, use 6mm template to pulverize it, in forced ventilation loft drier, at 150 ℃, be dried 60 minutes, then the roller mill that is continuously 1000 μ m, 600 μ m and 400 μ m by gap width grinds, and the material grinding by screening and particle size range is adjusted to 150 to 850 μ m.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 29.2g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that the absorbed dose (AUL0.7psi) under 16.3g/g and high pressure is 8.0g/g.
Embodiment 7
Step is as embodiment 6, and difference is that polyreaction carries out under the existence of 1ppm thiodiphenylamine (based on vinylformic acid meter).Even if 30 minutes post polymerization temperature are lower than 100 ℃ and also do not reach 100 ℃ after 60 minutes, and make mixture not process because polymerization is insufficient again.
This embodiment is illustrated under the existence of inhibition of impurities, and monomer solution no longer can carry out polymerization.
Embodiment 8
The polyreaction (embodiment 7) that repetition is carried out under 1ppm thiodiphenylamine exists, but the consumption of initiators for polymerization improved.Below use: 0.89g peroxy-disulfuric acid sodium water solution (concentration 5.0 % by weight), 0.57g aqueous ascorbic acid (concentration 0.5 % by weight) and 0.57g aqueous hydrogen peroxide solution (concentration 0.5 % by weight).As described in example 7 above further after aftertreatment, the centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 31.9g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that the absorbed dose (AUL0.7psi) under 17.7g/g and high pressure is 7.8g/g.
Embodiment 9
The polyreaction (embodiment 7) that repetition is carried out under 1ppm thiodiphenylamine exists, but the consumption of initiators for polymerization improved.Below use: 1.01g peroxy-disulfuric acid sodium water solution (concentration 5.0 % by weight), 0.65g aqueous ascorbic acid (concentration 0.5 % by weight) and 0.65g aqueous hydrogen peroxide solution (concentration 0.5 % by weight).As described in example 7 above further after aftertreatment, the centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 32.0g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that the absorbed dose (AUL0.7psi) under 13.1g/g and high pressure is 7.6g/g.
Embodiment 10
The polyreaction (embodiment 7) that repetition is carried out under 1ppm thiodiphenylamine exists, but the consumption of initiators for polymerization improved.Below use: 1.17g peroxy-disulfuric acid sodium water solution (concentration 10.0 % by weight), 0.75g aqueous ascorbic acid (concentration 1.0 % by weight) and 0.75g aqueous hydrogen peroxide solution (concentration 1.0 % by weight).In polyreaction, cause latter 30 minutes, polymerization temperature is approximately 105 ℃ and at approximately 105 ℃ of actual T that reach
maximum.As described in example 7 above further after aftertreatment, the centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 35.8g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that the absorbed dose (AUL0.7psi) under 9.3g/g and high pressure is 7.5g/g.
Table 3: compensation inhibition of impurities (thiodiphenylamine)
*) not exclusively polymerization
The impact that this form illustrates inhibition of impurities can compensate by the amount of adjusting initiator.
Embodiment 11
By 96g vinylformic acid, the 785g sodium acrylate aqueous solution (concentration 37.3 % by weight), 115g deionized water and 0.88g3 heavily ethoxylation three vinylformic acid glyceryl ester (concentration approximately 85 % by weight) by passing into nitrogen, within 30 minutes, remove atmosphericoxygen.The initiated polymerization by add 2.34g peroxy-disulfuric acid sodium water solution (concentration 2.0 % by weight), 2.40g aqueous ascorbic acid (concentration 0.2 % by weight) and 2.00g aqueous hydrogen peroxide solution (concentration 1.0 % by weight) in 2 liters of plastic containers.Reach the maximum polymerization temperature (T of approximately 110 ℃
maximum).Reach T
maximumafter 60 minutes, shift out polymer gel, with mincer, use 6mm template to pulverize it, in forced ventilation loft drier, at 150 ℃, be dried 60 minutes, then the roller mill that is continuously 1000 μ m, 600 μ m and 400 μ m by gap width grinds, and the material grinding by screening and particle size range is adjusted to 150 to 850 μ m.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 35.4g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 9.6g/g and extractable content are 13.9 % by weight.
Embodiment 12
Step is as embodiment 11, and difference is that polyreaction carries out under the existence of 10ppm vinyl carbinol (based on vinylformic acid meter).The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 36.6g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 8.5g/g and extractable content are 14.1 % by weight.
Embodiment 13
Step is as embodiment 11, and difference is that polyreaction is carried out under the existence of 10ppm vinyl carbinol (based on vinylformic acid meter) and the amount of triple ethoxylations three vinylformic acid glyceryl ester used is increased to 0.97g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 34.1g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 10.9g/g and extractable content are 11.5 % by weight.
Embodiment 14
Step is as embodiment 11, and difference is to be aggregated in carries out under the existence of 10ppm vinyl carbinol (based on vinylformic acid meter) and the amount of triple ethoxylations three vinylformic acid glyceryl ester used is increased to 1.06g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 33.7g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 12.0g/g and extractable content are 11.4 % by weight.
Table 4: compensating regulation impurity (vinyl carbinol)
This form illustrates and regulates the impact of impurity to compensate by the amount of adjusting linking agent.
Embodiment 15
Step is as embodiment 11.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 35.6g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 9.2g/g and extractable content are 13.5 % by weight.
Embodiment 16
Step is as embodiment 11, and difference is that polyreaction carries out under the existence of 10ppm propenal (based on vinylformic acid meter).The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 37.4g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 8.4g/g and extractable content are 14.7 % by weight.
Embodiment 17
Step is as embodiment 11, and difference is that polyreaction is carried out under the existence of 10ppm propenal (based on vinylformic acid meter) and the amount of triple ethoxylations three vinylformic acid glyceryl ester used is increased to 0.97g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 35.5g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 9.8g/g and extractable content are 12.1 % by weight.
Embodiment 18
Step is as embodiment 11, and difference is that polyreaction is carried out under the existence of 10ppm propenal (based on vinylformic acid meter) and the amount of triple ethoxylations three vinylformic acid glyceryl ester used is increased to 1.06g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 34.7g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 10.3g/g and extractable content are 11.3 % by weight.
Table 5: compensating regulation impurity (propenal)
This form illustrates and regulates the impact of impurity to compensate by the amount of adjusting linking agent.
Embodiment 19
Step is as embodiment 11.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 35.5g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 9.5g/g and extractable content are 13.2 % by weight.
Embodiment 20
Step is as embodiment 11, and difference is to be aggregated under the existence of 10ppm2-furfural (based on vinylformic acid meter) carries out.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 36.2g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 9.2g/g and extractable content are 14.0 % by weight.
Embodiment 21
Step is as embodiment 11, and difference is that polyreaction is carried out under the existence of 10ppm2-furfural (based on vinylformic acid meter) and the amount of triple ethoxylations three vinylformic acid glyceryl ester used is increased to 0.97g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 34.6g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 10.4g/g and extractable content are 12.5 % by weight.
Embodiment 22
Step is as embodiment 11, and difference is to be aggregated in carries out under the existence of 10ppm2-furfural (based on vinylformic acid meter) and the amount of triple ethoxylations three vinylformic acid glyceryl ester used is increased to 1.06g.The centrifugal retention volume (CRC) of the water-absorbing polymeric particles of gained is 34.0g/g thus, and the absorbed dose under pressure (AUL0.3psi) is that 10.7g/g and extractable content are 12.0 % by weight.
Table 6: compensating regulation impurity (2-furfural)
This form illustrates and regulates the impact of impurity to compensate by the amount of adjusting linking agent.
Claims (12)
1. a method for continuous production of water-absorbent polymer, comprises that by a kind of monomer solution or suspension polymerization, to obtain polymer gel, described monomer solution or suspension comprise:
The vinylformic acid that a) can be neutralized at least partly,
B) at least one linking agent,
C) at least one initiator,
D) optionally one or more can with the ethylenically unsaturated monomers of acrylic acid copolymer, and
E) one or more water-absorbing polymers optionally,
The polymer gel of gained is dry, dry polymer gel is pulverized to obtain polymer beads and by the polymer beads classification of gained, wherein vinylformic acid is without interruption, and vinylformic acid without interruption has and is less than the purity of 99.8 % by weight and acrylic acid purity without interruption changed and is less than 2 % by weight in 24 hours.
2. method according to claim 1, wherein vinylformic acid without interruption has the purity of 90 to 99 % by weight.
3. method according to claim 1 and 2, wherein acrylic acid purity without interruption changed and is less than 0.5 % by weight in 24 hours.
4. according to the method in any one of claims 1 to 3, wherein vinylformic acid without interruption comprises
The adjusting impurity of-at least 0.0005 % by weight, and/or
The inhibition of impurities of-at least 0.00005 % by weight, and/or
The crosslinked impurity of-at least 0.005 % by weight.
5. according to the method described in any one in claim 1 to 4, wherein vinylformic acid without interruption comprises
The adjusting impurity of-0.001 to 0.05 % by weight, and/or
The inhibition of impurities of-0.0001 to 0.05 % by weight, and/or
The crosslinked impurity of-0.05 to 0.5 % by weight.
6. according to the method described in any one in claim 1 to 5, wherein vinylformic acid a) has been neutralized to 25 to 95mol% degree.
7. according to the method described in any one in claim 1 to 6, wherein impurity is water, acetic acid, propenal, formic acid, formaldehyde, propionic acid, furans-2-formaldehyde, furans-3-formaldehyde, phenyl aldehyde, protoanemonin, maleic anhydride, toxilic acid, diacrylate, allyl acrylate, phenylformic acid, hydroquinone monomethyl ether, quinhydrones and/or thiodiphenylamine.
8. according to the method described in any one in claim 1 to 7, wherein the moisture content of water-absorbing polymeric particles is 15 % by weight at the most.
9. according to the method described in any one in claim 1 to 8, wherein the particle diameter of at least 95 % by weight water-absorbing polymeric particles is for being greater than 150 μ m.
10. according to the method described in any one in claim 1 to 9, wherein the particle diameter of at least 95 % by weight water-absorbing polymeric particles is no more than 850 μ m.
11. according to the method described in any one in claim 1 to 10, and wherein the centrifugal retention volume of water-absorbing polymeric particles is 15g/g at least.
12. according to the method described in any one in claim 1 to 11, and wherein water-absorbing polymeric particles is crosslinked afterwards by surface.
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| CN114096606A (en) * | 2019-07-05 | 2022-02-25 | 住友精化株式会社 | Crosslinked polymer gel, method for producing same, monomer composition, and method for producing crosslinked polymer particles |
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| Publication number | Publication date |
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| EP2714755B1 (en) | 2017-04-26 |
| EP2714755A1 (en) | 2014-04-09 |
| JP6188683B2 (en) | 2017-08-30 |
| CN103562240B (en) | 2017-02-15 |
| WO2012164081A1 (en) | 2012-12-06 |
| JP2014515430A (en) | 2014-06-30 |
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